Esta dissertação está dividida em duas partes, intituladas: 1) reações de expansão de anel promovidas por iodo(III) e 2) estudos visando à oxidação de octalinas e metileno-ciclo-hexanos. Na primeira parte foram estudadas reações de expansão de anel de álcoois alílicos protegidos com TMS (trimetilsilano) e de benzo-metilenos com iodo(III). O principal reagente de iodo hipervalente utilizado foi o hidróxi(tosilóxi)iodobenzeno (HTIB). O comportamento de cinco álcoois alílicos protegidos foi investigado: dois contendo metoxilas no anel aromático, um contendo bromo no anel aromático, um derivado de tetra-hidroquinolina e um derivado de benzofurano. Verificou-se a formação de produtos com anéis de sete membros em rendimentos de cerca de 70%. As condições reacionais empregadas foram: temperaturas de -72 a 50 °C, MeOH ou mistura MeOH/AcOEt e tempos de reação de 2-6 h. É importante frisar a formação de uma benzo-azepina. Além disso, empregando um substrato aromático rico em elétrons, obtivemos um produto de desaromatização, em uma reação pouco usual para as condições empregadas. Nas reações dos benzo-metilenos com iodo(III) foram testados quatro substratos: um derivado de benzo-furano, um derivado de indol, um benzo-pirano e uma benzoxepina. As reações foram realizadas em MeOH, à t.a., em 20-60 min. Os produtos de expansão de anel heterocíclicos foram formados em rendimentos de aproximadamente 60%, sendo destaque a obtenção de anéis de oito membros com oxigênio. Finalmente, na segunda parte do trabalho, foram realizados estudos visando à contração de anel de uma cis-octalina e à expansão de um metileno-ciclo-hexano utilizando HTIB. Os testes apontaram para a formação de produtos de adição e de contração de anel em quantidade de traço. / This Master\'s Thesis is divided in two parts, titled: 1) ring expansion reactions promoted by iodine(III) and 2) studies toward the oxidation of octalins and methylenecyclohexanes. On the first part, ring expansion reactions of TMS (trimethylsilane) protected allylic alcohols and benzomethylenes promoted by iodine(III) were studied. The main hypervalent iodine reagent employed was hydroxy(tosyloxy)iodobenzene (HTIB). Five protected allylic alcohols were explored: two containing methoxy groups on the aromatic ring, one containing a bromine on the aromatic ring, one tetrahydroquinoline derivative, and one benzofurane derivative. Seven-membered ring compounds were formed in nearly 70% yield. Reaction conditions were: temperature from -72°C to 50 °C, MeOH or MeOH/AcOEt as solvent and reaction time of 2-6 h. The formation of a benzoazepine needs to be highlighted. In addition, using an electron-rich aromatic substrate, a dearomatization product was obtained. This is an unusual result considering the conditions used. Regarding reactions of benzomethylenes with iodine(III), the behavior of four substrates was studied: a benzofuran derivative, an indole derivative, a benzopyran and a benzoxepin. Reactions were performed in MeOH, at r.t. in 20-60 min. The ring expanded products were obtained with yields of approximately 60%. The formation of eight-membered rings O-heterocycle was achieved. Finally, on the second part of this work, reactions of HTIB with a cis-octalin and with a methylenecyclohexane were studied aiming ring contraction and expansion products, respectively. Tests showed the formation of addition and ring contraction products as traces

Esta dissertação está dividida em duas partes, intituladas: 1) reações de expansão de anel promovidas por iodo(III) e 2) estudos visando à oxidação de octalinas e metileno-ciclo-hexanos. Na primeira parte foram estudadas reações de expansão de anel de álcoois alílicos protegidos com TMS (trimetilsilano) e de benzo-metilenos com iodo(III). O principal reagente de iodo hipervalente utilizado foi o hidróxi(tosilóxi)iodobenzeno (HTIB). O comportamento de cinco álcoois alílicos protegidos foi investigado: dois contendo metoxilas no anel aromático, um contendo bromo no anel aromático, um derivado de tetra-hidroquinolina e um derivado de benzofurano. Verificou-se a formação de produtos com anéis de sete membros em rendimentos de cerca de 70%. As condições reacionais empregadas foram: temperaturas de -72 a 50 °C, MeOH ou mistura MeOH/AcOEt e tempos de reação de 2-6 h. É importante frisar a formação de uma benzo-azepina. Além disso, empregando um substrato aromático rico em elétrons, obtivemos um produto de desaromatização, em uma reação pouco usual para as condições empregadas. Nas reações dos benzo-metilenos com iodo(III) foram testados quatro substratos: um derivado de benzo-furano, um derivado de indol, um benzo-pirano e uma benzoxepina. As reações foram realizadas em MeOH, à t.a., em 20-60 min. Os produtos de expansão de anel heterocíclicos foram formados em rendimentos de aproximadamente 60%, sendo destaque a obtenção de anéis de oito membros com oxigênio. Finalmente, na segunda parte do trabalho, foram realizados estudos visando à contração de anel de uma cis-octalina e à expansão de um metileno-ciclo-hexano utilizando HTIB. Os testes apontaram para a formação de produtos de adição e de contração de anel em quantidade de traço. / This Master\'s Thesis is divided in two parts, titled: 1) ring expansion reactions promoted by iodine(III) and 2) studies toward the oxidation of octalins and methylenecyclohexanes. On the first part, ring expansion reactions of TMS (trimethylsilane) protected allylic alcohols and benzomethylenes promoted by iodine(III) were studied. The main hypervalent iodine reagent employed was hydroxy(tosyloxy)iodobenzene (HTIB). Five protected allylic alcohols were explored: two containing methoxy groups on the aromatic ring, one containing a bromine on the aromatic ring, one tetrahydroquinoline derivative, and one benzofurane derivative. Seven-membered ring compounds were formed in nearly 70% yield. Reaction conditions were: temperature from -72°C to 50 °C, MeOH or MeOH/AcOEt as solvent and reaction time of 2-6 h. The formation of a benzoazepine needs to be highlighted. In addition, using an electron-rich aromatic substrate, a dearomatization product was obtained. This is an unusual result considering the conditions used. Regarding reactions of benzomethylenes with iodine(III), the behavior of four substrates was studied: a benzofuran derivative, an indole derivative, a benzopyran and a benzoxepin. Reactions were performed in MeOH, at r.t. in 20-60 min. The ring expanded products were obtained with yields of approximately 60%. The formation of eight-membered rings O-heterocycle was achieved. Finally, on the second part of this work, reactions of HTIB with a cis-octalin and with a methylenecyclohexane were studied aiming ring contraction and expansion products, respectively. Tests showed the formation of addition and ring contraction products as traces

Bioinspirierte Polymere, die die Multidomänenstruktur des Muskelproteins Titin imitieren, wurden auf Grundlage von zuvor synthetisierten, zyklischen Präpolymeren, die Wasserstoffbrückenbindungen-tragende Monomere enthalten, hergestellt und hinsichtlich ihrer mechanischen Eigenschaften untersucht.  Zunächst wurde die Ringexpansionspolymerisation (REP) zur Erzeugung zyklischer Makromoleküle, die auf einer von Nishikubo et al. entwickelten, lebenden Gruppentransferpolymerisation von Thiiranmonomeren mit Acylgruppen-tragenden Initiatoren basiert, eingehend untersucht. Im Speziellen wurde ein System, bestehend aus dem zyklischen Initiator 2,4-Thiazolidindion (TZD) und Derivaten desselben, dem Katalysator Tetrabutylammoniumchlorid, verschiedenartig substituierten Thiiranmonomeren 2-(Phenoxymethyl)thiiran (PMT), 2-Methylthiiran (MT), 2-(tert-Butoxymethyl)thiiran (TBMT), 2-((o-Methylphenoxy)methyl)thiiran (MPMT) und dem Lösungsmittel N-Methylpyrrolidin-2-on verwendet. Bei der Insertion der Monomere MT, TBMT und MPMT in TZD, die unter guter Kontrolle des Polymerisationsgrads und der Dispersität stattfand, wurde eine Verschmelzung der Ringe zu größeren Ringstrukturen mit einem Verschmelzungsgrad von bis zu zwei, bei Verwendung von PMT sogar von bis zu vier beobachtet. Der Grad dieser Verschmelzung nahm im Fall von PMT mit zunehmender Monomerkonzentration, zunehmendem molaren Monomer-zu-Initiator-Verhältnis und zunehmender Reaktionstemperatur ab, während er bei den anderen Monomeren keine Konzentrations- und Temperaturabhängigkeit zeigte. Durch Anpassung der Molmassenverteilungen mittels einer Summe von Gauß-Funktionen im Fall der PMT-Polymere konnte die zeitliche Änderung der molaren Anteile der verschiedenen Ringspezies verfolgt werden. So wurden für Polymerkonzentrationen von 14 bis 52 Gew-% Geschwindigkeitskoeffizienten der Verschmelzung, die sich über Größenordnungen von 10^(−2) bis 10^(−6) L/mol/s erstrecken, ermittelt. Bei Verwendung von in 3-Position substituierten TZD-Derivaten wurde eine Zunahme der Anzahl verschmolzener Makrozyklen von bis zu sieben festgestellt. Die Bildung zyklischer Strukturen wurde mittels Massenspektrometrie und rasterkraftmikroskopischer (AFM) Aufnahmen gezeigt.  Neben den Homopolymerisationen wurden zyklische (AB)n-Multiblockcopolymere aus MT und PMT mit bis zu acht aus der Ringverschmelzung resultierenden Blöcken synthetisiert. Sie zeigten im Zugversuch, aufgrund der verschiedenen Topologien, im Vergleich zu linearen Diblockcopolymeren ähnlicher Zusammensetzung, deutliche Unterschiede in der maximalen Zugdehnung und der Zähigkeit.  Weiterhin wurden die eingangs erwähnten bioinspirierten Polymere durch Kombination von zyklischen und linearen Segmenten hergestellt und auf ihre mechanischen Eigenschaften untersucht. Dazu wurden zyklische (ABC)n-Multiblockcopolymere, die zusätzlich einen kurzen Block des Monomers Ethyl-2-(4-(thiiran-2-ylmethoxy)benzamido)acetat (ETBAA) enthielten, der zur Ausbildung selbstkomplementärer Wasserstoffbrückenbindungen in der Lage ist, synthetisiert. Diese Präpolymere wurden mittels 1,3-dipolarer Cycloaddition in einer Polyadditionsreaktion mit einem niedermolekularen, bifunktionellen Verknüpfungsagens oder mit monofunktionellem Poly-n-butylacrylat (PBA) bzw. Polymethylacrylat (PMA), welche mittels RAFT-Polymerisation hergestellt wurden, verknüpft. So konnte im ersten Fall eine Poly-Ringpolymer-Topologie mit bis zu 19 nachgewiesenen Wiederholeinheiten und im zweiten Fall ein Polymer mit Kette–Ring–Kette-Topologie erhalten werden.  Untersuchungen der Proben im Zugversuch zeigten beim Kette–Ring–Kette-Polymer bis auf eine höhere Elastizität keine verbesserten Materialeigenschaften im Vergleich zum linearen PMA-Präpolymer. Die Poly-Ringpolymere hingegen zeigten im Gegensatz zu den Ringpolymeren ein einzigartiges Spannungs-Dehnungsverhalten, bessere Elastizitätseigenschaften und eine Erhöhung der anwendbaren Spannung bei gleicher Dehnung. Dies wurde durch den Einfluss inter- und intramolekular ausgebildeter physikalischer Bindungen durch die enthaltenen selbstkomplementären Wasserstoffbrückenbindungsmotive hervorgerufen. Eines der untersuchten Poly-Ringpolymere zeigte aufgrund der Ausbildung eines reversiblen physikalischen Netzwerkes sogar ein Formgedächtnis und die Fähigkeit zu einer partiellen Selbstheilung.

L’Analyse Linéaire de Stabilité a été largement utilisée afin de décrire l’évolution du mode dominant des instabilités pour différentes configurations. Toutefois, plusieurs observations expérimentales et numériques ont démontré l’existence de distributions de longueurs inter-strictions, prémices aux distributions de tailles de fragments. Une extension de cette utilisation classique de l’Analyse Linéaire de Stabilité dédiée à l’extension d’un barreau en traction a été proposée afin de rendre compte de la contribution de l’ensemble des modes de perturbation sur le profil final des strictions. Cette approche, correspondant physiquement au cas des anneaux fins en expansion, est à même de déterminer une distribution de longueurs inter-strictions. En se basant sur les mêmes outils mathématiques que ceux ayant permis d’étendre l’analyse linéaire de stabilité, une nouvelle approche numérique a été suivie afin de déterminer le temps d’apparition et le nombre de strictions en fonction de la vitesse de chargement, de l’amplitude et de la taille de cellules de perturbations. Une comparaison, en termes de distribution de longueurs inter-strictions, a été par la suite obtenue entre résultats analytiques et numériques. De bonnes corrélations ont été observées. Le développement d’un montage expérimental d’expansion d’anneaux par forces électromagnétiques a été entamé au cours de ce travail de thèse. Lors de sa finalisation, il devrait permettre une validation expérimentale des approches développées dans les domaines numériques et analytiques / Linear Stability Analysis has been widely used in order to describe the evolution of the dominant necking pattern in different configurations. However, experimental and numerical observations have demonstrated that a distribution of internecking lengths is obtained instead of a unique dominant pattern. In this work, an extension of the classical Linear Stability Analysis applied to the dynamic extension of a round bar case has been developed to take into account the contribution of all perturbation modes on the final necking pattern. This approach, corresponding physically to the case of thin ring expansion, is able to determine a distribution on internecking distances. Based on the same mathematical tools that was developed for the extension of the linear stability analysis, a new numerical approach has been followed to determine the number and the onset time of necking with respect to loading velocity, amplitude and cell size of the perturbations. A comparison, in terms of distributions of inter-necking distance, has been carried out between analytical and numerical results. Good correlations have been observed. An electromagnetic ring expansion experimental device has been proposed during this work. Whith some additional development, it should enable to validate experimentally the working assumptions developed in the numerical and analytical studies

There is an increasing trend towards advancing the understanding and development of ethylene oligomerization catalysts, both in academia and industry. The metal of choice in this chemistry is invariably chromium, which has shown great versatility in selective trimerization/tetramerization, non-selective oligomerization and polymerization of ethylene. While much success has been achieved in ethylene trimerization, the same con not be said about tetramerization catalysis. Aminophosphine based ligands have demonstrated their ability towards selective 1-octene production, however, the popular PNP catalyst is able to achieve only 70% selectivity. In order to explore the possibility of developing and enhancing the selectivity of chromium based ethylene tetramerization catalyst, this thesis work was undertaken. The ligand systems we chose for our work were bidentate aminophosphine based (PN(CH2)nNP), which has yielded interesting selective oligomerization. Subtle modifications were found to result in drastic changes in selectivity, from tetramerization (PN(CH2)3NP) to trimerization (PN(CH2)2NP). We managed to successfully develop the first truly selective (over 90%) 1-octene catalyst with polymer-free behavior. Further modifications on the ligand framework, where one atom of Si was used to link the two NP units, resulted in non-selective oligomerization, in which case we determined that the oxidation-state of chromium is a key player. We explored other modifications on our selective ligands in which one of the arms on the bidentate ligand was replaced with a base-donor amine, phosphine or pyridine, and resulted in interesting selectivity changes. The final modification that we tested was a novel N(CH2)2P ligand and found it to be a highly active, non-selective oligomerization catalyst.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

There is an increasing trend towards advancing the understanding and development of ethylene oligomerization catalysts, both in academia and industry. The metal of choice in this chemistry is invariably chromium, which has shown great versatility in selective trimerization/tetramerization, non-selective oligomerization and polymerization of ethylene. While much success has been achieved in ethylene trimerization, the same con not be said about tetramerization catalysis. Aminophosphine based ligands have demonstrated their ability towards selective 1-octene production, however, the popular PNP catalyst is able to achieve only 70% selectivity. In order to explore the possibility of developing and enhancing the selectivity of chromium based ethylene tetramerization catalyst, this thesis work was undertaken. The ligand systems we chose for our work were bidentate aminophosphine based (PN(CH2)nNP), which has yielded interesting selective oligomerization. Subtle modifications were found to result in drastic changes in selectivity, from tetramerization (PN(CH2)3NP) to trimerization (PN(CH2)2NP). We managed to successfully develop the first truly selective (over 90%) 1-octene catalyst with polymer-free behavior. Further modifications on the ligand framework, where one atom of Si was used to link the two NP units, resulted in non-selective oligomerization, in which case we determined that the oxidation-state of chromium is a key player. We explored other modifications on our selective ligands in which one of the arms on the bidentate ligand was replaced with a base-donor amine, phosphine or pyridine, and resulted in interesting selectivity changes. The final modification that we tested was a novel N(CH2)2P ligand and found it to be a highly active, non-selective oligomerization catalyst.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Le taux de déformation des matériaux est élevé pendant le soudage / formage à grande vitesse, le découpage, le sertissage, etc. Les propriétés des matériaux sous déformation à grande vitesse ne suivent pas la même loi que dans le cas de chargement quasi statiques. La caractérisation des matériaux à taux de déformation important est assez difficile et nécessite des équipements sophistiqués. Grâce au développement de la technologie de formage électromagnétique, le test d'expansion d'anneau électromagnétique présente un grand potentiel à utiliser pour caractériser les matériaux à haute vitesse de déformation. Pendant le test d’expansion de l’anneau électromagnétique, la pièce à usiner peut atteindre une vitesse d’expansion de l’ordre de 100m/s et une vitesse de déformation de 104 s-1. Par conséquent, ce test peut être utilisé pour prédire les paramètres du matériau, tels que la dureté et la ductilité à déformation à grande vitesse. Pour d’atteindre cet objectif, un modèle approprié décrivant le processus est nécessaire. Ce modèle doit contenir un couplage électromagnétique-mécanique-thermique pour bien décrire le problème multi-physique. Il existe deux méthodes principales de modélisation dans la littérature, viz. Les méthodes semi-analytiques et les méthodes des éléments finis (parfois combinées avec la méthode des éléments limitants). Les méthodes semi-analytiques nécessitent un temps de calcul court mais offrent une faible précision par rapport aux méthodes des éléments finis. Cependant, en raison de la complexité du couplage multi-physique, l’erreur de calcul est difficile à estimer. De plus, les déformations hétérogènes ainsi que les états de contrainte compliqués peuvent influencer l’identification. Dans ce sens, cette thèse s’est principalement concentrée sur les méthodes d’analyse et de modélisation du test d’expansion d’anneau électromagnétique, incluant les comportements locaux et les phénomènes dynamiques à l’aide des outils expérimentaux et numériques. Par ailleurs, cette thèse comprend aussi le développement d’un méthode semi-analytique permettant le couplage multi-physique, ce qui a été validé par un modèle numérique idéal et par des tests expérimentaux. Les résultats expérimentaux ont été obtenus à l’aide d’une caméra à grande vitesse et du vélocimétrie photovoltaïque Doppler (PDV) pour différents cas tests. Ils ont été utilisés pour déterminer les paramètres du processus et du matériau à l’aide des modèles numériques. Les modèles adaptés pour analyser les états de contrainte et de déformation durant le test d’expansion d’anneau montrent que ce dernier n’est pas un test de traction uniaxial pur comme revendiqué par les chercheurs. En outre, le phénomène de vibration qui se produise de la récupération élastique a été étudié par simulations multi-physiques et par systèmes PDV. Cette étude de récupération élastique permet de mieux comprendre les paramètres influençant du test, ce qui pourrait être utilisé pour contrôler le rebond dans d’autres processus électromagnétique. La méthode de modélisation semi-analytique pour le test d’expansion de l’anneau électromagnétique, qui comprend quatre parties de calcul (partie mécanique, thermique, force de Lorentz et courant de Foucault), a été analysée à l’aide de simulations numériques. Les résultats obtenus ressemblent étroitement aux résultats obtenus par un test idéal et un test expérimental. L’analyse d’erreur des différents aspects physiques permet d’améliorer la précision de calcul semi-analytique, ce qui pourrait être utilisé comme outil supplémentaire d’obtention rapide des paramètres de contrôle dans les tests. Il pourrait aussi être utilisé pour l’identification des paramètres des matériels à déformation à grande vitesse. / High stain rate material deformations are prevalent during high speed impacts, high speed forming/welding, cutting, crimping, blast etc. Characteristics of materials under high strain rate deformation do not follow the same as it occurs under the quasi-static loading conditions. However, characterization of materials under high strain rate deformation is always challenging and it requires sophisticated equipment. Thanks to the development in electromagnetic forming technology, the electromagnetic ring expansion test shows a great potential to be used to characterize materials under high strain rate conditions. During the electromagnetic ring expansion test, the workpiece can reach deformation velocities in the order of 100 m/s and a strain rate of up to 104 s-1. Consequently, this test can be used to predict the material parameters such as the strain rate hardening and ductility under extremely high strain rates (strain rates in the order of 103 – 104 s-1). In order to achieve this goal, an appropriate model is required to describe the process. The model should contain an electromagnetic-mechanical-thermal coupling to obtain the accurate multi-physics nature of the problem. There exist two main modeling methods in literature, viz., the semi-analytical methods and finite element methods (sometime combined with boundary element method). Normally, the semi-analytical methods require short calculation time while it provides lower accuracy in comparison with finite element methods. However, due to the complexity of multi-physics coupling, the calculation error is difficult to be analyzed. Moreover, errors in calculation and identification assumptions may also result from heterogeneous deformations or localized specific phenomena (such as local necking at multi points or electric current localization, skin effect, edge effect of Lorentz force etc.) that could influence identification work as well as stress and strain states. Therefore, this thesis mainly focused on the analysis and modeling methods of ring expansion test including local behaviors and dynamic phenomena with the help of experimental and numerical tools. Moreover, this thesis also includes a development of a semi-analytical method with multi-physics coupling capabilities, which has been validated using a theoretical model and experimental frameworks. Experimental measurements were obtained using high-speed cameras and photonic Doppler velocimetry (PDV) for various test cases are used together with numerical models to investigate the process and material parameters. The models used to analyze the stress and stain states during a ring expansion test show that the ring expansion test is not a pure uniaxial tensile test as claimed by researchers. Besides, another potential process behavior, the vibration phenomena that occurs during the elastic recovery was investigated using multi-physics simulations and PDV systems. This investigation of the elastic recovery helps to understand the potential influencing parameters of the test those are applicable and could be used to control the springback phenomenon during other electromagnetic forming processes. The semi-analytical modeling method for ring expansion test including four calculation parts (mechanical part, eddy current, Lorentz force calculation, thermal part) were analyzed with the help of numerical simulations. The results obtained from analytical work closely resemble with the numerical simulations for both theoretical model and an experimental case study. The error analysis of various physical aspects allows improving the accuracy of semi-analytical calculation that could be used as an additional platform to obtain rapid calculation of the test conditions. This semi-analytical method could be extended in the future to identify material parameters under high strain rate deformations.

There is an increasing trend towards advancing the understanding and development of ethylene oligomerization catalysts, both in academia and industry. The metal of choice in this chemistry is invariably chromium, which has shown great versatility in selective trimerization/tetramerization, non-selective oligomerization and polymerization of ethylene. While much success has been achieved in ethylene trimerization, the same con not be said about tetramerization catalysis. Aminophosphine based ligands have demonstrated their ability towards selective 1-octene production, however, the popular PNP catalyst is able to achieve only 70% selectivity. In order to explore the possibility of developing and enhancing the selectivity of chromium based ethylene tetramerization catalyst, this thesis work was undertaken. The ligand systems we chose for our work were bidentate aminophosphine based (PN(CH2)nNP), which has yielded interesting selective oligomerization. Subtle modifications were found to result in drastic changes in selectivity, from tetramerization (PN(CH2)3NP) to trimerization (PN(CH2)2NP). We managed to successfully develop the first truly selective (over 90%) 1-octene catalyst with polymer-free behavior. Further modifications on the ligand framework, where one atom of Si was used to link the two NP units, resulted in non-selective oligomerization, in which case we determined that the oxidation-state of chromium is a key player. We explored other modifications on our selective ligands in which one of the arms on the bidentate ligand was replaced with a base-donor amine, phosphine or pyridine, and resulted in interesting selectivity changes. The final modification that we tested was a novel N(CH2)2P ligand and found it to be a highly active, non-selective oligomerization catalyst.